Method of creaseproofing cellulosic fabrics by wet creaseproofing followed by dry creaseproofing and the resulting product



United States Patent Ofilice 3,175,874 Patented Mar. 30, 1965 3,175,874 METHOD OF CREASERROOFING CELLULOSEC FABRICS BY WET CREASEPROOFING FOL- LOWED BY DRY CREASEPRGOFENG AND THE RESULTlN G PRUDUCT Dmitry Michael Gagarine, Spartanburg, S.C., assignor to Deering Milliken Research Corporation, Pendlcton, S.C., a corporation of Delaware No Drawing. Filed Jan. 29, 1959, Ser. No. 78?,798 8 Claims. ((11. 8-4156) This invention relates to methods for treating textile fabrics containing cellulosic fibers and more particularly the invention relates to processes for imparting minimum care or wash and wear characteristics to textiles.

This is a continuation-impart of my copending applications S.N. 575,716, now US. Patent 2,985,501 and SN. 677,204, filed August 9, 1957, now abandoned.

It has previously been suggested that various resinous materials be applied to cellulosic fabrics to impart minimum care characteristics thereto and such fabrics have achieved a limited degree of commercial success. It is a characteristic of such fabrics, however, that they must normally be drip dried, or in other words, hung to dry while dripping wet in order for them to have a semblance of a pressed appearance when dry and this has limited the commercial acceptance thereof. Another disadvantage of prior art resin impregnated minimum care fabrics is that they have either a harsh hand or insufficient wrinkle resistance since it has been found that in order to impart even a relatively high degree of wrinkle resistance to a cellulosic fabric, it is normally necessary to apply such a large amount of resinous material that the hand of the treated fabric is rough. Further, even when large amounts of the resinous material are applied, the fabrics do not have as high a degree of wrinkle resistance as is desired, and large amounts of resin, applied to cotton fabrics, embrittle the fiber-s so as to make them unserviceable in normal wear.

According to this invention cellulosic fabrics having minimum care characteristics and which do not have the disadvantages of prior art cellulosic wash and wear resin treated fabrics are produced by a process which comprises treating a cellulosic fabric, either before or after a resin is applied, with an alkali catalyzed, cellulose cross linking agent which results in the cellulosic fibers being cross linked with linkages of from 3 to 15 carbon atoms in length. The reaction with the cellulose cross linking agent is conducted with the cellulosic fibers in a moist condition and while the cellulosic fibers are swollen by contact with a basic aqueous solution.

Fabrics produced according to this invention have nu merous advantages as compared to prior art resin impregnated cellulosic fabrics. For example, fabrics according to this invention have a much better hand than prior art fabrics because much smaller quantities of resin must be applied to obtain satisfactory wrinkle resistance, and a fabric can have imparted thereto by a process according to this invention more dry crease resistance with the application of only about 5% resin than can in many instances be imparted with prior art techniques by the application of 15% or more of the same resin. Another advantage of fabrics processed according to this invention is that they are more crease or wrinkle resistant than prior art fabrics for the reason that with a reasonable amount of resin applied according to this invention a degree of crease resistance can be imparted which it is substantially impossible to obtain by the use of even very large amounts of resins applied according to the procedures of the prior art. Still another advantage of fabrics processed according to this invention is that they need not be drip dried but can be washed in a conventional manner, centrifuged or wrung until only damp, and thereafter line dried or tumble dried to result in them having a pressed appearance. Other advantages of fabrics processed according to this invention will become apparent from the detailed description of the invention to follow.

Any cellulosic fabric to which resins can suitably be applied can normally be processed according to this invention, the term cellulosic being defined for purposes of this specification and claims to include unmodified cellulose and cellulose modified by ether-ification or esterification of a portion of the hydroxy groups. Examples of suitable fabrics include fabrics formed from natural cellulose fibers such as cotton and linen fabrics and fabrics formed from regenerated cellulose fibers such as viscous rayon fabrics. If desired, fabrics formed from cellulosic fibers in which the percentage of free hydroxy groups have been replaced by ester or ether groups can be processed according to this invention although it will be understood that the cellulosic fibers should be alkali insoluble, the phrase alkali insoluble being defined to mean, in this specification and claims, insoluble in 1% to 5% sodium hydroxide solution. Also, since the new process requires cross linking of the cellulosic fibers by reaction of a cross linking agent with free hydroxide groups of the cellulosic fibers, at least some free hydroxy groups must be present in order to obtain a satisfactory degree of cross linkage, but normally cellulosic fibers which contain as few as 1.8 free hydroxy groups per anhydro glucose unit result in suflicient cross linkage for satisfactory results. In View of the above it will be seen that cellulosic fabrics the fibers of which contain a limited number of acetyl groups, such as cellulose acetate fabrics of a relatively low lacetyl content, or fabrics the fibers of which contain a limited number of methyl ether groups, such as partially methylated cellulose, can be processed according to this invention under proper conditions, but that cellulosic fabrics the fibers of which have been fully ether-ified or esterified are not normally suitable for use in the process of this invention.

Satisfactory results, according to this invention, can also be achieved with fabrics partially composed of other than cellulosic materials, and this is particularly true if the non-cellulosic fibers have some minimum care characteristics of their own. For example, the minimum care characteristics of fabrics formed from a mixture of glycol-terephthalate fibers and cotton fibers can readily be increased by the process of this invent-ion even if the percentage of cotton fibers is as small as, for example, 10% and similar results can be obtained with fabrics formed from a mixture of nylon fibers and cellulosic fibers or a mixture of cellulosic fibers and polyacrylic fibers such as those sold under the trademark Orlon. Even when the non-cellulosic fibers when employed alone result in fabrics having no minimum care characteristics, fabrics containing a mixture of the same with cellulosic fibers can be caused to display minimum care characteristics by a process according to this invention if the fabric contains at least about by weight of cellulosic fibers.

The resinous materials which can be employed in the process of this invention and which will hereinafter be referred to simply as textile resins are low molecular weight (less than 1,000), water soluble, acid or acid salt catalyzed materials which are thermosetting at least in the presence of cellulosic materials as above defined. The largest class of resins within this group comprises the aminoplast resins formed by reacting compounds such as urea and melamine with formaldehyde, and specific examples of resins within this class include urea formaldehyde resins such as the resin commercially available from Rohm & Haas under the trade name of Rhonite 610; methyl ethers of urea formaldehydes such as the resin sold by Rohm & Haas under the trade name of R-2 Resin; acrolein urea formaldehyde resins; cyclic ethylene urea formaldehyde resins such as the resin sold by E. I. du Pont under the trade names of Zset and the resin sold by Rohm & Haas under the trade name of R1 Resin; trimethylol acetylene diurea; tetramethylol acetylene diurea; melamine formaldehyde resins such as the resins sold by Monsanto under the trade names Resloom H. P. and Resloom L. C.; methylated melamine formaldehyde resins such as the resins sold by American Cyanamid under the trade name of M-3 Resin, or the resin sold by Monsanto under the trade name of M-75 Resin; copolymers such as a copolymer of melamine formaldehyde and ethylene urea formaldehyde; and the resins known to the trade as urons, one of which has the formula:

In addition to resins of the above type, one can suitably employ epoxy resins which come within the general group set forth above and specific examples of suitable resins of this class include'the diglycidyl ether of ethylene glycol, the triglycidyl ether of glycerol, and the epoxy resin sold by Shell Chemical Company under the name of. Eponite 100. Still another class of resins which can suitably be employed are the triazinone resins and any member of this type of resins coming within the above defined group can give satisfactory results according. to the process of this invention. Still another resin which can be employed is tris (l-aziridinyl) phosphine oxide which is prepared by reacting three moles of ethyleneimine with one mole of POCl and which is known to the trade as APO Resin or Imine I. P. Resin. One need not employ a single resin material butcan employ blends of' resins of the above type or copolymers where available. Likewise, it is not necessary. that the resins be entirely free from water insoluble components since it has been found that dispersed particles of water insoluble materials in the resin solution are not deleterious even though any portion of the resin that is water insoluble does not contribute to the beneficial results obtainable according to this invention. Some of the commercially available resinous materials mentioned above contain small percentages of water insoluble polymeric materials and while an aqueous mixture of such resins can be filtered if desired, equally satisfactory results are generally obtained by employing the unfiltered material.

Suitable. acid catalysts for resins of the above types are well known in the art. Urea formaldehyde and melamine formaldehyde resins are best catalyzed by chloride or nitrate salts of hydroxyethyl amines such as monoethanol amine hydrochloride or 2 amino-2 methylpropanol nitrate. Cyclic ethylene urea formaldehyde resins, acetylene diurea formaldehyde and the uron resins are preferably catalyzed by zinc nitrate or by magnesium chloride. The epoxy resins are preferably catalyzed by acid fluoride salts, such as the catalyst compositions available from Shell Development Company under the trade names of Curing Agent 48 and Curing Agent 20. The above catalysts are all characterized by their ability to furnish hydrogen ions which are necessary for the condensation or etherification reactions taking place during the curing cycle. Generally any amount of catalyst up to about 5% by weight of the solution will give satisfactory results with the preferred range being from about 0.5% to 2% by weight of the resin solution.

The amount of resin which is applied to the textile fabric according to this invention can be varied within wide limits and the most advantageous amount is dependent upon a number of variables. For example, the amount of resin which can most advantageously be applied depends upon whether the resin is applied before or after the cross linking operation, the degree of cross linking of the cellulosic fibers effected during the cross linking operation, and the particular type of resin being employed. It is a general rule that the greater the degree of cross linkage, the smaller the amount of textile resin which can advantageously be employed, and one can obtain results by employing only a relatively small amount of resin on a highly cross linked cellulosic fabric which are comparable to those obtained by employing a relatively larger amount of textile resin on a cellulosic fabric the fibers of which have been cross linked to only a slight degree. In most instances, it is desirable to employ only a small amount of the resin material and from about 1% to 5% resin solids on the weight of the" fabric generally gives optimum results. Due to the synergistic action of the cross linking agent and the textile resin, the effectiveness of the textile resin is greatly increased as compared to prior art procedures of resin applications to cellulosic fabrics and satisfactory minimum care characteristics and wrinkle resistance can sometimes be obtained by the procedure of this invention employing as little as 0.5% resin solids, based on the weight of the fabric. At the other extreme, an amount of resin material equal in some instances to as much as 10% to 15% by weight of the fabric can be employed without imparting 'an unacceptable hand, but the use of such large amounts of resin is generally not necessary and is not economically desirable.

The textile resins employed according to this invention are, in each instance, water soluble and are applied in the form of an aqueous solution containing the desired amount of catalyst material. Conventional padding equipment is suitable for this operation and with such apparatus the textile fabric can be passed through an aqueous solution of the resin and thereafter extracted,

for example by being passed through squeeze rolls, to'

result in sufficient solution being picked up by the fabric to provide the desired amount of resin solids on the fabric. Following the resin application, the fabric is dried and cured at any suitable curing temperature. The most advantageous curing temperature depends upon the particular resin and catalyst employed, but as a general rule a curing temperature in the range from about C. to 200 C. and preferably between C. and 180 C. is satisfactory. The curing temperature should be maintained for from 10 seconds to 30 minutes with the preferred range being from 30 seconds to 5 minutes depending on the temperature, amount and type of catalyst, and the particular resin compound.

Any cellulose cross linking agent which is active under alkaline conditions and which results in cross linkages of from 3 to 15 carbon atoms in length can be employed in a process according to this invention, the phrase cellulose cross linking agent being defined to mean a compound having two or more connective groups or in other words, groups which are capable or potentially capable under alkaline conditions of reacting with the hydroxy groups of cellulose to form ether linkages. Normally the cross linking agent will have only two connective groups as above defined but in some instances the agent may suitably have as many as four connective groups. In saying that the cross linking agent results in cross linkages having from 3 to carbon atoms, it is not intended to exclude the possibility that the linkage formed by the cross linking agent contain elements other than carbon and, in fact, in all instances the cross linkage will contain oxygen since the cross linkage is a result of the etherification of hydroxy groups of the cellulose. bon, the linkage may also contain nitrogen, sulfur, silicon, or other polyvalent elements known to form stable organic linkages. Likewise, the cross linkage may contain substituent groups or side chains and examples of substituent groups which may be present include keto groups, hydroxy groups, halogen groups, and methyl groups, although the presence of such substituent groups is normally not desirable and in any case the number and size of substituent groups should not be such that the molecular weight of the polyvalent radical connecting the reactive groups of the cross linking agent is in excess of about 260. It should also be emphasized that the cross linking agent, while spoken of as having two or more reactive groups, need not possess groups, as it is initially employed in the process of this invention, which are capable of reacting directly with hydroxy groups since the reactive groups can suitably be transformed in situ as a result of the action of the basic catalyst to give connective groups capable of reacting with cellulose to give a polyether cross linkage.

Cross linking agents within the above general classification can be divided into three distinct classes. A first class comprises the polyepoxy cross-linking agents, e.g., diepoxybutane; the diglycidyl ether of ethylene glycol, propylene glycol, or diethylene glycol; the triglycidyl ether of glycerol; and the diglycidyl ether of bisphenol A, and compounds such as the above which have a halohydrin group in place of one or more of the epoxy groups, and compounds which have a halogen substituent on a carbon atom adjacent either an epoxy group or a halohydrin group. Examples of such compounds are epichlorohydrin, 1,2-dichloropropanol-3, 1-3-dibromo-propanel-2, and bis(1-chloro-2-hydroxy-n-propoxy)ethane. A second class of cross linking agents within the above general group includes the sulfone activated divinyl cross linking agents and suitable examples of this class of agents are divinyl sulfone, bis(vinyl sulfonyl)methane, and 1-4- b is(vinyl sulfony1)butane. A third class of cross linking agents are the carbonyl activated divinyl cross linking agents as illustrated by divinyl ketone, and octadiene- 1-2,7-8-dione-3-6. It will be notice that the cross linking agents of the last two classes, an activating group, Le, a sulfonyl or carbonyl group, is alpha to each vinyl group.

The amount of the alkali catalyzed cross linking agent reacted with the cellulosic fabric may be varied within relatively wide limits, but according to the process of this invention only a small degree of cross linkage is necessary. In some instances satisfactory results can be obtained by reacting a cellulosic fabric with only enough of the alkali catalyzed cross linking agent to theoreti cally result in as few as 0.0003 cross link per anhydro glucose unit, the phrase anhydro glucose unit being used in a generic sense to include instance where the hydroxy groups of the cellulosic material are in part etherified or esterified, and in most instances the reaction of the fabric with an amount of the cross linking agent capable of resulting in more than 0.08 cross link per anhydro glucose unit is not desirable. Best results are generally obtaind when the fabric is reacted with an amount of the alkali catalyzed cross linking agent theoretically capable of providing from 0.001 to 0.01 cross link per anhydro glucose unit. The cross linking agent or mixture of cross linking agents is preferably applied in relatively pure form, or in other words, without the In addition to oxygen and can use of a solvent or diluent, but due to the small degree of cross linkage necessary in accordance with this invention, the cross linking agent can be employed in an 'orangic solvent or in most instances even in the form of an aqueous solution.

The alkali catalyzed cross linking agent can be applied by any suitable procedure and where solutions of the cross linking reagent are employed, the solution is preferably applied by padding followed by extraction to remove excess solution. In instances where the pure cross linking reagent is employed it is generally preferable to apply same to the fabric by a distributing technique so that a limited quantity of the reagent can be applied and excessive cross linkage avoided. Distribution of the pure reagent upon the fabric can be achieved by the use of spray, Scotch rolls, or other apparatus of this type which permits one to evenly distribute a relatively small quantity of a reagent upon a textile fabric.

The basic material employed as a catalyst for the cross linking reaction is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide but other basic materials such as sodium silicate and quaternary ammonium bases as illustrated by trimethylphenylammonium hydroxide and tetramethylammonium hydroxide can also be employed with less satisfactory results. The basic catalyst for the cross linking reaction is employed in the form of an aqueous solution of a concentration which provides an active concentration on the fabric of from 1% and preferably from 5% to 15% by weight. For example, when the basic solution is applied to a dry fabric, the concentration of the basic solution is preferably from 5% to 15% by weight. The basic solution may be applied to the fabric either before or after the cross linking agent is applied and if precautions are taken to prevent excess reaction of the cross linking agent with water, the basic catalyst and the cross linking agent can even be applied to the fabric simultaneously. Generally, it is preferred that the basic catalyst be applied prior to the application of the cross linking agent by means of conventional padding equipment which permits the fabric to be immersed in an aqueous solution of the base and thereafter squeezed or extracted to remove excess basic solution. Alternatively, the basic catalyst solution can be applied by means of sprays, Scotch rolls, or in instances where the cross linking agent is applied first, the fabric can simply be immersed in an excess of the basic solution of a proper concentration and the reaction allowed to take place during the time the fabric is so immersed.

It a high degree of cross linkage is to be achieved with some cross-linking agents, e.g., those employed in US. Patent 2,985,501, the total amount of water present in and on the fabric during the cross linking reaction is of great importance and should be limited so that the amount of water is equal to not more than about 100% of the weight of the dry fabric and preferably not more than about of the Weight of the dry fabric. Under these conditions, the cross linking reaction can not be conducted with the fabric immersed in an aqueous solution and must be conducted with the fabric removed from a body of liquid and containing a total amount of liquid not in excess of that amount capable of being retained by the fabric when not immersed in a body of liquid. This can be readily accomplished by forming the fabric into a roll or the like and enclosing a roll of fabric in any suitable manner in a gaseous atmosphere to prevent loss of reagents.

As previously mentioned, the cross linking reaction is conducted with the cellulosic fibers in a swollen condition and more specifically the reaction should be conducted with the fibers swollen so that they have a diameter of at least about 25% in excess of the diameter of the fibers in a dry condition. It is not normally necessary, however, to measure the degree of swelling of the fibers for the reason that in substantially all instances the application of a basic solution of a concentration as setforth above results in adequate swelling, but the necessity of the fibers being in a swollen condition does requlre that the alkali catalyzed reaction be conducted at a temperature below the boiling point of the basic aqueous solution at the particular pressure employed. Normally, the reaction will be conducted at a temperature below about 100 C. to avoid the use of super-atmospheric pressure but super-atmospheric pressure can be employed if for some reason it is desired to employ reaction temperatures appreciably in excess of 100 C. The preferred temperature for conducting the alkali catalyzed cross linking reaction is usually room temperature or the temperature which is developed as a result of the reaction.

The time required for the alkali catalyzed cross linking reaction depends upon the temperature, the type and amount of basic catalyst employed, and the particular cross linking agent used. Under conditions favoring a fast reaction and with highly reactive cross linking agents, sufficient cross linkage can be obtained in only to seconds, but in most instances at least about 5 minutes to 2 hours should be allowed for the cross linking reaction to occur. If only suflicient cross linking agent is applied to the fabric to give the desired degree of cross linkage, there is no need to control reaction time other than to insure that adequate time is allowed and a period of 24 or even 48 hours can be provided; but if the cross linking reaction is conducted with the fabric immersed in an excess of reagent, precautions must be exercised to avoid excessive cross linkage of the fabric. For this reason a procedure which involves applying limited quantities of the alkali catalyzed cross linking reagent to the fabric is greatly preferred.

The invention will now be illustrated by the following examples in which all parts are by weight unless otherwise indicated.

EXAMPLE I V A sample of type 180 cotton sheeting (96 warp threads per inch of width and 84 threads per inch of length), desized, bleached, and dried, is cut into three pieces which are labeled A, B, and C. Sample A is immersed into 14% sodium hydroxide solution, squeezed out between rubber rolls to a-wet pickup of 80%, and the open, wet fabric is then passed over a print roller to deposit and distribute on the fabric 6%, based on dry fabric weight, of 1,3 dichloropropanol-Z. (For further details as to procedure for distributing small quantities of reagents on fabrics, reference may be made to copending US, application Serial Number 575,716.) Sample A is then batched into a smooth roll, wrapped with a polyethylene sheet and allowed to remain for four hours. It is then washed and dried. A portion of sample A is cut off and labeled D and the remainder is dipped into a water solution containing 5% solids of a methylated melamine formaldehyde resin (M-75, Monsanto Chemical Co.) and 2% zinc nitrate. It is then squeezed between rubber rolls to remove excess liquids and to result in a wet pickup of about 70%, thus depositing 3.5% resin solids on the weight of the dry fabric. The fabric is then dried at room temperature and cured 10 minutes at 150 C.

Sample B is passed through the same resin solution as sample A squeezed, dried, and cured exactly as sample A.

Sample C is dipped into an aqueous solution containing 10% resin solids, and 2% zinc nitrate and is then squeezed between rubber rolls to remove excess liquid and to provide a wet pickup of 70% so that the sample contains 7% resin solids based on dry fabric weight. It is then dried at room temperature and cured 10 minutes at 150 Cfin the same manner as samples A and B.

Samples A, B, C, and D are then placed into an air conditioned room maintained at 70 F. with a relative humid of 65%. After 48 hours conditioning, the

Average of W+F Crease Resistance, Degrees Filling Tear Strength (Elmendorf) Percent Resin Solids Sample Control Sample A Sample B Sample O Sample D It will be seen from the results given in the above table that the synergistic effect between cross linking and resin treatment, greatly increased the effectiveness of the resin treatment. With 3.5% resin solids, sample A had an appreciably greater crease resistance than samples Band C despite the fact that sample C contained 7% resin solids. This is quite surprising in view of the fact that cross linking alone did not materially change the crease resistance of the fabric from that of the untreated sample. In addition, the tear strength of sample A was substantially greater than that of sample C.

EXAMPLE II A sample of type 180 all cotton sheeting, which has been desized, bleached and dried, is cut into three pieces which are labeled A, B, and C. Sample A is treated with 14% sodium hydroxide and 1,3-dichloropropanol-2 in exactly the same manner as sample A in Example I and a portion of the sample is cut off and labeled D. The remainder of sample A is then dipped into an aqueous solution containing 3% dimethylol cyclic ethylene urea and 2% zinc nitrate and the thus impregnated fabric is squeezed between rubber rolls to a wet pickup of about 70%. It is thereafter air dried and cured 10 minutes at C.

Sample 13 is padded with a 3% resin solution as above which is not reacted with 1,3-dichloropropanol.

Sample C is padded through an aqueous solution containing 6% dimethylol cyclic ethylene urea and 2% zinc nitrate and is squeezed to a 70% pickup. It is then dried and cured in the same manner as samples A and B.

Samples A, B, C, and D are then conditioned 48 hours as in Example I and tested.

The following results were found in an experiment conducted according to the above example.

Table I] Percent Resin Solids Crease Resistance Tear Strength (Filling) Sample Sample D 0 Table II clearly shows that the combination treatment with a cyclic ethylene urea formaldehyde and an alkali catalyzed cross linking agent greatly increases the efiectiveness of the resin and in addition provides a greater tear strength for a given degree of crease resistance.

EXAMPLE III resistance of the thus processed fabric is greatly increased and the fabric can be line dried without drip drying to give a pressed appearance.

EXAMPLE IV An 80 square cotton fabric is processed according to the procedure of Example 111 except that 3% of a polyepoxy resin sold by Shell Development Company under the trade name of Eponite 100 is applied in place of the uron resin and as an alkali catalyzed cross linking agent there is employed 4% of the diglycidyl ether of ethylene glycol in place of the divinyl ketone of Example III. The resulting fabric has a high degree of crease resistance, a relatively high crease resistance to strength ratio as compared to a fabric impregnated by prior art procedures with materials of this type, and can be line dried to give a pressed appearance.

EXAMPLE V A sample of type 180 sheeting is immersed into a freshly prepared aqueous solution containing 5% divinyl sulfone and 2% sodium hydroxide, and the cloth is thereafter squeezed between rubber rolls to remove excess solution such that the pickup is about 80%. The wet fabric is rolled up into a neat roll, wrapped in polyethylene plastic and aged for thirty minutes. It is then neutralized with dilute acetic acid, thoroughly washed and dried. The fabric is then padded with a 3% aqueous solution of dimethylol methyl triazinone resin containing 1% zinc nitrate, dried and cured for minutes at 150 C. The thus treated fabric has excellent minimum care characteristics.

EXAMPLE VI A desized and bleached piece of 80 square cotton fabric is treated with 8% aqueous solution of cyclic ethylene urea formaldehyde resin containing 1% zinc nitrate catalyst, dried and cured for two minutes at 170 C. The fabric is then immersed into an aqueous solution containing 6% divinyl sulfone and 2% sodium hydroxide, squeezed out between rubber rolls to a pickup of 60%, batched into a roll, wrapped with polyethylene plastic and allowed to stand 30 minutes. The fabric is then washed thoroughly and dried. The thus treated fabric has excellent crease resistance.

EXAMPLE VII Example VI is repeated except that the fabric is treated with a 10% aqueous solution of dimethyl ether of dimethylol ethyl triazinone resin containing 2% monoethanol amine hydrochloride instead of cyclic ethylene urea resin of Example V1. The results are substantially the same as in Example VI.

EXAMPLE VIII A fabric is treated with dimethylol methyl triazinone resin as in Example VII and the cured fabric is immersed into an aqueous solution containing 14% 1,3-dichloropropanol-2 maintained at 75 C. The fabric is squeezed between rubber rolls to a pickup of 60% and is subsequently immersed in an aqueous solution containing 10% sodium hydroxide and 15% sodium sulfate. This alkaline solution is maintained at 90 C. and the resin treated fabric is maintained under the surface of the alkaline liquid for a period of 30 seconds. It is then squeezed out by the rubber rolls to remove excess liquid and is washed until free of alkali. The thus treated fabric has excellent wrinkle resistance.

EXAMPLE IX A plain weave cotton fabric made of 30s yarn, and containing 80 picks, and 80 ends to the inch, is impregnated with an aqueous solution containing 15% 1-3-dichloropropanol-2. It is then squeezed out between rubber rolls to a pickup of 80% and immersed into a hot (90 C.) aqueous solution containing 15% by weight of sodium hydroxide and 18% sodium chloride. The fabric is kept retained in said alkaline solution for a period of one minute, and is thereafter removed and thoroughly washed and dried. The fabric is then immersed in an aqueous solution containing 4% tetramethylol melamine and 1% of ethanol amine hydrochloride, squeezed out between rubber rolls to a pickup of dried and cured for zlWO minutes at 160 C. The thus treated fabric is suitable for wash and wear applications.

The procedure when employing other alkali catalyzed cross linking agents or other acid catalyzed textile resins is substantially the same as illustrated in the above examples.

Having thus described my invention and several specific embodiments thereof, what I desire to claim and secure by Letters Patent is:

1. A method for imparting minimum care characteristics to cellulosic textile fabrics the cellulose fibers of which have an average of at least 1.8 free hydroxy groups per anhydro-glucose unit which comprises the combination of steps of contacting the fabric, under aqueous alkaline conditions, with a textile creaseproofing chemical cross-linking agent for the cellulose fibers of the fabric and an alkaline catalyst for the reaction, and chemically cross-linking with the cross-linking agent a sufficient portion of the free hydroxy groups of the cellulosic fabric while the fabric is in an essentially water wet, swollen condition and in an essentially wrinkle-free condition whereby wet crease resistance is imparted to the fabric, and thereafter in a separate step also applying to said fabric a textile crease-proofing resin and an acid acting catalyst for the resin and curing said resin on the fabric while said fabric is in an essentially dry condition at elevated temperatures whereby dry crease resistance is imparted to the fabric.

2. A method according to claim 1 wherein the cellulosic fabric is cotton.

3. A process for imparting fiat drying properties to a cellulosic fabric Whose cellulosic fibers have an average of at least about 1.8 free hydroxy groups per anhydroglucose unit which comprises the steps of first applying to said fabric a total amount of water equal to at least 15 but less than by weight of the dry weight of the fabric, a strong base selected from the group consisting of alkali metal hydroxides, alkali metal salts which form alkali metal hydroxides in aqueous solution, and quaternary ammonium hydroxides, the amount of said base, on a dry weight basis and calculated as NaOI-I, coustituting not less than about 1% by weight and not more than about 15 by weight of the total water present, and at least about 5% but not more than about 30% by Weight of the celluiosic fibers of a cellulose creaseproofing chemical cross-linking agent selected from the group consisting of polyepoxy compounds, monoepoxy compounds having a halogen substituent on a carbon atom adjacent the epoxy group, and halohydrins having a halogen substituent on a carbon atom adjacent the halohydrin group, which produce cross linkages of from 3 to 15 carbon atoms in length and a molecular weight of less than 260, and chemically cross-linking with the cross-linking agent a sufficient portion of the free hydroxy groups of the cellulosic fabric While the fabric is in an essentially water wet, swollen condition and in an essentially wrinkle-free condition whereby the Wet crease resistance of said fabric is improved and thereafter applying to the cross-linked fabric a textile creaseproofing resin and an acidaacting catalyst for the resin, and curing the resin on the fabric while said fabric is in an essentially dry condition at an elevated temperature whereby the dry crease resistance of said cross-linked fabric is improved so that the fabric can be washed with centrifuging and then line or tumble dried to provide a pressed appearance thereto without ironing,

4. A method according to claim 3 wherein said crosslinking agent is a dihalopropanol.

5. A method according to claim 4 wherein said crosslinking agent is 1,3-dichloropropanol-2.

References Cited in the file of this patent UNITED STATES PATENTS Fuller July 7, 1942 Pfetfer Dec. 17, 1946 12 Schoene Oct. 3, 1950 Beer July 1, 1952 James June 1, 1954 Suen Jan. 10, 1956 Schroeder Dec, 18, 1956 Schroeder June 4, 1957 Marsh June 17, 1958 DAd amo June 2, 1959 Gagarine May 23, 1961 FOREIGN PATENTS Great Britain Aug. 2, 1939 Great Britain Apr. 13, 1955 

1. A METHOD FOR IMPARTING MINIMUM CARE CHARACTERISTICS TO CELLULOSIC TEXTILES FABRICS THE CELLULOSE FIBERS OF WHICH HAVE AN AVERAGE OF AT LEAST 1.8 FREE HYDROXY GROUPS PER ANHYDRO-GLUCOSE UNIT WHICH COMPRISES THE COMBINATION OF STEPS OF CONTACTING THE FABRIC, UNDER AQUEOUS ALKALINE CONDITIONS, WITH A TEXTILE CREASEPROOFING CHEMICAL CROSS-LINKING WITH THE CROSS-LINKING AGENT A SUFFICIENT PORTION OF THE FREE HYDROXY GROUPS OF THE CELLULOSIC FABRIC WHILE THE FABRIC IS IN AN ESSENTIALLY WATER WET, SWOLLEN CONDITION AND IN AN ESSENTIALLY WRINKLE-FREE CONDITION WHEREBY WET CREASE RESISTANCE IS IMPARTED TO THE FABRIC, AND THEREAFTER IN A SEPARATE STEP ALSO APPLYING TO SAID FABRIC A TEXTILE CREASE-PROOFING RESIN AND AN ACID ACTING CATALYST FOR THE RESIN AND CURING SAID RESIN ON THE FABRIC WHILE SAID FABRIC IS IN AN ESSENTIALLY DRY CONDITION AT ELEVATED TEMPERATURES WHEREBY DRY CREASE RESISTANCE IS IMPARTED TO THE FABRIC. 